Diazacyanine dyestuffs cations



United States Patent DIAZACYANINE DYESTUFFS CATIONS Hans Baumann and Dieter Leuchs, Ludwigshafen (Rhine), Germany, assignors to Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany N Drawing. Filed Sept. 23, 1958, Ser. No. 762,713

Claims priority, application Germany Oct. 24, 1957 6 Claims. (Cl. 260-305) This invention relates ,to new diazacyanine dyestufi cations.

The new dyestutf cations have the general formula:

in which D represents an atomic bridge which cornpletes the heterocyclic ring to form a thiazole or benzthiazole, R represents a low molecular weight aliphatic radical, R represents a hydrogen atom or an aliphatic or aromatic radical, R represents a hydrogen atom or a low molecular weight alkyl radical, A represents a divalent aliphatic, aromatic or aliphatic-aromatic radical which may also contain hetero atoms and Z represents an amino group.

The new dyestufi cations are derived from thiazoles or benzthiazoles. They have as a common feature an amino group Z which is situated outside the color-producing system. This amino group Z may be a primary, secondary or tertiary group with aliphatic radicals with up to carbon atoms, a mono-, dior hydroxy-alkylamino group or a heterocyclie amino group, such as a monoor di-methylamino group, a diethylamino, methylhydroxyethylamino, methylpropylamino, pyrrolidino, piperidino or morpholino group.

The other'substituents indicated in the general formula may be considerably varied without departing from the scope of the invention. Thus the radical R may be an alkyl group with up to 5 carbon atoms, such as a methyl, ethyl or butyl group. R may be a hydrogen atom, an unsubstituted or substituted hydrocarbon radical, for example an aliphatic radical with up to 5 carbon atoms or an aromatic radical with up to carbon atoms, the unsubstituted or substituted component of a heterocyclic ring, such as a methyl, ethyl, propyl, hydroxyalkyl, such as hydroxyethyl or hydroxyamyl radical, a phenyl radical, an alkylphenyl, a hydroxyphenyl radical or the saturated part of a 1,2,3,4-tetrahydroquinoline or hydroxytetrahydroquinoline radical. The symbol R stands for a hydrogen atom or an alkyl radical with up to 4 carbon atoms, such as a methyl or ethyl radical. The divalent radical A, which separates the amino group Z from the color-producing system, may also be of quite different nature. Thus A can be an unsubstituted or substituted alkylene radical with up to 5 carbon ,atoms, a hydroxyalkylene radical with up to 5 carbon atoms, the divalent radical of an alipahtic ether with up to 6 carbon atoms, an unsubstituted or substituted arylene radical with up to 10 carbon atoms, an aralkylene radical with up to 10 carbon atoms, a radical in which an unsubstituted or substituted alkylene group with up to 4 carbon atoms is connected through a hetero atom,'a carboxylic acid ester or a carboxylic acid amide group with an arylene group, such as an; ethylene, propylene, amylene, hydroxyproice pylene, hydroxybutylene or phenylene radical, a radical of the formula The rings of the new dyestufl cations may contain one or more mainly neutral substituents, such as alkyl groups, aryl groups, alkylamino, arylamino, acylamino, alkyl ether, alkylsulfone, sulfonic acid dialkylamido, catboxylic acid ester, carboxylic acid amido or cyano groups and/ or V Instead of the free hydrazones and amines, their more stable mineral acid salts may be used.

The diazacyanine dyestuif cations can be precipitated from their solution in the form of salts with inorganic or organic anions by acidification.

Hydrazones suitable for the production of the new dyestuif cations according to this process are for example 3 methyl 4 phenylthiazolone (2) -hydrazone- 3 methylbenzthiazolone (2) hydrazone, 3 ethylbenzthiazolone (2) hydrazone, 3 methyl 6 rnethoxybenzthiazolone (2) hydrazone, 3 methyl 6 chlorbenzthiazolone (2) hydrazone, 3 methyl 6 phenylaminobenzthiazolone (2) hydrazone, 3 methyl 6- acetylaminobenzthiazolone-(2)-hydrazone.

As amines capable of coupling there may be used for example N.N dimethyl-N'-(3 methylphenyDethylene diamine, N.N-diethy1-N'-(3-methoxypheny1)-ethylene diamine, N.N-dimethyl-N-phenylethylene diamine, N.N.N'- triethyl-N'-phenylethylene diamine, N.N-di-beta-hydroxyethyl N methy1-N'-phenylethylene diamine, N .N-dimethyl-N-beta-hydroxyethyl-N'-pheny1ethy1ene diamine, N.N-dimethyl N beta hydroxyethyl-N'-phenyl-l.3-diaminopropane, N.N-dimethyl-N'-ethyl-N'-phenyl 1.3-diaminopropanol-Z, N-butyl N- (beta-piperidinoethy1)-3- amino 1 methylbenzene, N-(beta-diethylaminoethyD- diphenylamine, N-(beta dimethy1aminoethyl)-4-ethoxydiphenylamine, 4-((beta-dimethylaminoethyl) amino)- diphenylamine, l-(gamma-aminopropyl)-2-phenylindole, 1- gamma-aminopropyl) l .2. 3-.4-tetrahydro quinoline.

In the second method for the production of the new diazacyaninedye stuff cations, a Z-aminothiazole which is not substituted on the ring nitrogen atom is first diazotized by known methods and coupled with the above-mentioned amines capable of coupling, to form an azo dyestuff. This azo dyestuff is then alkylated at temperatures of 10 to 130 0., especially 30 to 80 C., on the nitrogen atom of the thiazole ring with an alkylating agent and the new diazacyanine dyestufi cation thus obtained.

As diazotizable Z-aminothiazoles there may be men tioned: Z-aminothiazole, Z-amino-4.5-dimethylthiazole, 2-amino-4-phenylthiazole, Z-amino 4 (3'-nitrophenyl)- thiazole, 2-arnino 5 nitrothiazole, 2-amino-5-cyanothiazole, 2-amino-6-methyl-benzthiazole, 2-amino-6-rnethoxybenzthiazole, 2-amino-6-ethoxybenzthiazole, Z-amino- 4-methyl-6-chlorbenzthiazole.

Suitable alkylating agents are for example alkyl'halides, dialkyl sulfates or alkyl esters of organic sulfonic acids, such as, methyl bromide, ethyl chloride, dimethyl sulfate, diethyl sulfate and methyl-para-toluene sulfonate.

The diazacyanine dyestuff cations have good solubility in water in the form of their neutral salts With inorganic or organic anions. In particular, the acid salts which The following examples will further illustrate this invention but the invention is .not restricted to these examples. The parts specified in the examples are parts by weight and the percentages are percentages by weight.

Example ,1

A solution of 18 parts of N.N.N'-trimethyl-N'-,phenylethylene diamine in 100 parts of methanol is added to.

. aqueous solution of ferricchloride and 160 parts of a 50% aqueous sodium acetate solution are dripped in simultaneously. After the reaction, 40 parts of a 'S-normal hydrochloric acid and 200 parts of a saturated aqueous potassium chloride solution are added. The precipitate V is filtered off, washed with potassium chloride solution form by adding on an equivalent of an inorganic or and dried at C. in vacuo. 41 parts of the salt of the dyestutf cation of the formula:

dyeings on polyacrylonitrile, can be obtained in a correspending way: 5

D Example Formula polgz i t x yl nltrile fibers s H 2 eB/ blue-violet.

' OHz-CHz-N 7 I OHa-CH2O H O 2H5 S a cam-NH reddish blue.

adv-m0 N\ CHz-C Hz-N N HaC I 2H: 0 H;

C=NN= N CH-CHN H o T C H3 0 H S 5 blue.

69 CH C=NN= N a 63 C Hg-C Hn-N -H N S 6 H 0 0 Q reenish blue.

69/ 0 Ha g N/ CHa-OHr-N-H CH l 8 a E 1 For ula i i 8H1 m x i hiriifileis s\ t 7 blue.-

QHrCHg-N -H on. i 8; CH reddish blue.

UHr-CHOH-CH -n Example 9 S C H 18 parts of Z-amino-dmethoxybenzthiazole are di- Q/ a a C=N- N C2115 azotized 1n the usual way with mtrosyl sulfuric acid and coupled with a sulfuric acid aqueous solution of 24 parts N OHTCHFN When 2 $11.

of N.N.N-triethy1 N'-phenylethylene' diamine. coupling is ended, it is neutralized with aqueous sodium hydroxide solution, filtered by suction and washed on the filter. The dried dyestuif is dissolved in 250 parts of dimethyl formamide and, while stirring, 13.5 parts of dimethyl sulfate are added. It is heated to 90 to 100 C. until a pure blue solution has been formed and then poured into 2000 parts of water. By adding sodium chloride, the dyestufi salt is deposited, isolated and dried.

56 parts of the salt of the dyestufi cation of the formula:

and the chloride anion are obtained. It dissolves in water with a pure blue color. From a neutral, acetic acid or sulfuric acid dyebath, very pure greenish blue dyeings which exhibit excellent fastness to light and wet treatment are obtained on afabric of the COPOIYIHBI' of of dyeings on polyacrylonitrile, can be obtained in a corresponding way:

Dyeing on Example Formula polyacrylonitrile fibers l on. H e/ 10 [I C=N-N N CH; blue-violet.

HO I "Hz CH,CH:N\

CH: v GHr-CHz-OH 11 H3O q; reddish blue CHr-CHz-N H CH 12 3 (B greenish C=N-N=C =N N blue. CH: 43H;

CH 13 B 00 4 69 Do. CH:CHr-N\ 01H H; S\ H 14 H 0 0 6 turquoise. C=N-N N NHOHrOHa-N\ 1H: CH:

2. The diazacyanine dyestuif cation of the formula:

53 C Ha I 3. The diazaeyanine dyestuff cation of the formula:

CHa-CHz-N i CH 0113 C2 5 C H;

.5. The diazacyam'ne dyestutf cation of the formula:

CH3 CHz-CHa-N 6. The diazacyanine dyestufi cation of the general for in which: D'represents a divalent radical forming to gether with the structure of the above formula a member selected from the group consisting of thiazole, benzthiazole, thiazole substituted on a carbon atom in D of the above formula by a member selected from the group consisting of methyl, ethyl, phenyl; nitrophenyL'nitro and cyano, and benzthiazole substituted on a carbon atom in D of the above formula by a member selected from the group consisting of methyl; ethyl, methoxy, ethoxy, phenylamino, acetylamino and chloro; R represents lower alkyl with up to 5 carbon atoms; R represents a member selected from the group consisting of hydrogen, phenyl, lower alkyl with up'to 5 carbon atoms, monohydroxy-lowerr alkyl with up to '5 carbon atoms and further members in which R is a divalent radical selected from the group consisting of -t-CI-ll=OH--, -CH --CH --CH and r OH -oH, -t 1H-oH- said divalent radical being connected at one end to the nitrogen atom :23 shown in the above formula and at the other end to the quinoid ring adjacent to the position occupied by said nitrogen atom; R representsa member selected from "the group consisting of hydrogen and lower alkyl with up to 4 carbon atoms; A represents a divalent radical selected from the group consisting of lower alkylone with up to 5 carbon atoms and monohydroxy-lower alkylene with up to 5 canbon atoms; and Z represents a member containing up to 5 carbon atoms selected from the group consisting of -NH secondary and tertiary lower alkylamino and monohydroxy-lower alkylamino, pyrrolidino, morpholino and piperidino.

References Cited in the file of this patent UNITED STATES PATENTS 2,441,612 Argyle et a1. May 18, 1948 

6. THE DIAZACYANINE DYESTUFF CATION OF THE GENERAL FORMULA 